Fungicidal compositions

ABSTRACT

The invention provides a fungicidal composition comprising at least one systemic, contact and/or soil fungicide and at least one acrylic acid morpholide derivative of the general formula in which R1 represents a hydrogen, chlorine or bromine atom, a trifluoromethyl, trifluoromethoxy, C3-C7 alkyl, C3-C5 alkoxy, C3-C6 alkenyl, HClFC-CF2O-, HClC=CClO-, cyclohexyl, cyclopentenyl, cyclohexenyl, phenyl, 4-chlorophenyl, 4-ethylphenyl, 4-chlorobenzyl or 4-chlorophenylthio group or a phenoxy group optionally substituted by one or more substituents selected from fluorine and chlorine atoms and methyl and ethoxycarbonyl groups and R2 represents a hydrogen atom, or R1 represents a hydrogen atom and R2 represents a 3-phenoxy group.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation application of Ser. No.08/118,243, filed Sep. 9, 1993, now abandoned, which is a divisionalapplication of Ser. No. 07/735,308, filed Jul. 24, 1991, now U.S. Pat.No. 5,262,414, which is a continuation application of Ser. No.07/505,583, filed Apr. 6, 1990, now abandoned, which is a divisionalapplication of Ser. No. 07/149,516, filed Jan. 28, 1998, now U.S. Pat.No. 4,923,866 which is a continuation of application Ser. No.06/913,136, filed Sep. 29, 1986, now U.S. Pat. No. 4,753,934, which is acontinuation of application Ser. No. 06/583,770, filed Feb. 27, 1984,now abandoned.

This invention relates to fungicidal compositions comprisingcombinations of fungicidal substances and, in particular, to thepreparation and use of compositions comprising certain acrylic acidmorpholide derivatives in combination with certain systemic, contactand/or soil fungicides.

Many different compounds are known for use as systemic, contact or soilfungicides. Examples of some such compounds which are availablecommercially can be found in "The Pesticide Manual", Eighth Edition,1987, edited by Charles R. Worthing and S. Barrie Walker, published byThe British Crop Protection Council.

It is also known that certain acrylic acid morpholide derivatives areeffective in combating a variety of phytopathogenic fungi. Examples ofsuch compounds are disclosed in EP-A1-0 120 321 and EP-A1-0 219 756.

It has now been discovered that the fungicidal effect of some of theseacrylic acid morpholides can be improved to a surprising extent if theyare used in combination with certain systemic, contact and/or soilfungicides.

According to the present invention there is therefore provided afungicidal composition comprising at least one systemic, contact and/orsoil fungicide and at least one acrylic acid morpholide derivative ofthe general formula ##STR2## in which R₁ represents a hydrogen, chlorineor bromine atom, a trifluoromethyl, trifluoromethoxy, C₃ -C₇ alkyl, C₃-C₅ alkoxy, C₃ -C₆ alkenyl, HClFC--CF₂ O--,HClC═CCl--, cyclohexyl,cyclopentenyl, cyclohexenyl, phenyl, 4-chlorophenyl, 4-ethylphenyl,4-chlorobenzyl or 4-chlorophenylthio group or a phenoxy group optionallysubstituted by one or more substituents selected from fluorine andchlorine atoms and methyl and ethoxycarbonyl groups and R₂ represents ahydrogen atom, or R₁ represents a hydrogen atom and R₂ represents a3-phenoxy group.

It is preferred that R₁ represents a chlorine or bromine atom or atrifluoromethyl, trifluoromethoxy, propyl, butoxy, phenyl,4-chlorophenylthio, 4-chlorophenoxy, 4-methylphenoxy or4-ethoxycarbonphenoxy group, especially a chlorine or bromine atom or atrifluoromethyl, trifluoromethoxy, phenyl or 4-chlorophenoxy group.

It is also preferred that R₂ represents a hydrogen atom.

A particularly preferred sub-group of compounds is that in which R₁represents a chlorine atom or a phenyl group and R₂ represents ahydrogen atom.

Examples of the preparation of acrylic acid morpholide derivatives offormula I are given in EP-A1-0 120 321 and EP-A1-0 219 756.

Examples of systemic, contact and soil fungicides which are particularlysuitable for use in a composition according to the present invention aregiven below:

(A) Systemic fungicides

1. Benalaxyl

2. Cymoxanil

3. Cyprofuram

4. Metalaxyl

5. Ofurace

6. oxadixyl

7. Fosetyl-aluminium

8. Phosphorous acid and its salts.

(B) Contact fungicides

1. Anilazine

2. Captafol

3. Captan

4. Chlorothalonil

5. Dichlofluanid

6. Dithianon

7. Fentin acetate

8. Folpet

9. Copper

10. Copper oxychloride

11. Mancozeb

12. Maneb

13. Metiram

14. Propineb

15. Zineb

(C) Soil fungicides

1. Etridiazole

2. Fenaminosulf

3. Hymexazol

4. Propamocarb

5. Prothiocarb

The generic names given in groups A, B and C above represent compoundshaving the following IUPAC names:

Group A

1. Methyl N-phenylacetyl-N-2,6-xylyl-D,L-alaninate.

2. 1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea.

3. (+)-α- N-(3-chlorophenyl)cyclopropanecarboxamido!-γ-butyrolactone.

4. Methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-D,L-alaninate.

5. (±)-α-2-chloro-N-2,6-xylylacetamido-γ-butyrolactone.

6. 2-methoxy-N-(2-oxo-1,3-oxazolidin-3-yl)acet-2',6'-xylidide.

7. Aluminium tris(ethyl phosphonate).

Group B

1. 4,6-dichloro-N-(2-chlorophenyl)-1,3,5-triazin-2-amine.

2. 1,2,3,6-tetrahydro-N-(1,1,2,2-tetrachloroethylthio)phthalimide.

3. 1,2,3,6-tetrahydro-N-(trichloromethylthio)phthalimide.

4. Tetrachloroisophthalonitrile.

5. N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulphamide.

6. 2,3-dicyano-1,4-dithia-anthraquinone.

7. Triphenyltin acetate.

8. N-(trichloromethylthio)phthalimide.

10. Dicopper chloride trihydroxide.

11. Manganese ethylenebis(dithiocarbamate) complex with zinc salt.

12. Manganese ethylenebis(dithiocarbamate).

13. Zinc ammoniate ethylenebis(dithiocarbamate)-poly (ethylenethiuramdisulphide).

14. Polymeric zinc propylenebis(dithiocarbamate).

15. Zinc ethylenebis(dithiocarbamate).

Group C

1. 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole.

2. Sodium 4-dimethylaminobenzenediazosulphonate.

3. 5-methylisoxazol-3-ol.

4. Propyl 3-(dimethylamino)propylcarbamate.

5. S-ethyl(3-dimethylaminopropyl)thiocarbamate.

Of the systemic fungicides listed above, cymoxanil, fosetyl-aluminium,phosphorous acid and disodium phosphite are especially preferred and, ofthe contact fungicides listed above, chlorothalonil, dithianon andmancozeb are especially preferred for use in a composition according tothe present invention.

Some formula I compounds may also be combined to advantage withcompounds from Group A and Group B in a triple combination.

The improved effect of the compositions according to the presentinvention is thought to be due to synergism or breakdown of resistance.Another advantage is the broader spectrum of activity.

The compositions according to the invention can be used preventively orcuratively in a number of crops such as grapes, potatoes, tomatoes,cucumbers, tobacco, hops, pumpkins, cabbages and other vegetables,rubber, citrus fruits, avocados, pineapples, cocoa, roses, carnationsand other ornamental plants.

Combinations between compounds of formula I and compounds from groups Aand B are also particularly suitable for the control of fungal diseasesin grapes if the vine is already infected (curative treatment).

The quantities of active ingredients used in combined products accordingto the invention depend on the application rates for the compounds whenused on their own, but also on the proportion of one product to anotherand on the degree of synergism. Also of relevance is the target fungus.The relative proportions between formula I compounds and group A, B andC compounds may in extreme cases be between 1:160 and 60:1 based onparts by weight of active ingredient but are preferably between 1:20 and10:1.

Specific information on the quantity proportions is given below.

Formula I compounds are applied in concentrations of between 25-1000ppm, and preferably between 100-500 ppm, whereas the amounts ofcompounds combined with them should preferably be as follows (allfigures in ppm):

Group A

Compound 1,3,4,5,6: 20-500 (50-200)

Compound 2: 50-500 (80-150)

Compound 7: 100-2500

Compound 8: 100-4000 (600-2000)

Group B

Compound 1,2,4,5,14: 400-2000 (500-1500)

Compound 3,8: 800-3000 (100-2000)

Compound 6: 150-700 (250-500)

Compound 7: 250-800 (400-700)

Compound 9,10,11,12,13,15: 1200-3000 (1500-2000)

Group C

Substance 1,3: 300-2000 (500-1500)

Substance 2,4,5; 500-1500 (800-1200)

A composition according to the invention may further comprise a carrier,the active ingredients being present in a total amount of 0.5 to 95% byweight.

A carrier in a composition according to the invention is any materialwith which the active ingredient is formulated to facilitate applicationto the locus to be treated, which may for example be a plant, seed orsoil, or to facilitate storage, transport or handling. A carrier may bea solid or a liquid, including abmaterial which is normally gaseous butwhich has been compressed to form a liquid, and any of the carriersnormally used in formulating fungicidal compositions may be used.

The compositions according to the invention may be formulated assolutions, emulsions, wettable powders, suspensions, powders, dusts,pastes, soluble powders, granulates, suspension or emulsifiableconcentrates or aerosols. Solutions and powders contained in polymercapsules are also suitable, as are natural or synthetic materials orcarriers impregnated with the active substance.

These formulations are manufactured in the usual way, such as by mixingthe active substances with liquid solvents and/or solid carriers, whereappropriate with the addition of surfactants ie. emulsifiers and/ordispersants, stabilisers, wetting agents, binding agents, dyes andodorisers. The invention therefore also includes a method for making afungicidal composition as defined above which comprises bringing theactive ingredients into association with at least one carrier.

If water is used as a solvent or diluent, organic solvents may also beused as auxiliary solvents or anti-freeze additives. Suitable organicsolvents include aromatics such as benzene, xylene, toluene,alkylbenzenes, alkylnaphthalenes and chlorinated aromatics; chlorinatedaliphatic hydrocarbons such as chlorobenzene, chloroethylene,trichloroethane, methylene chloride, chloroform, carbon tetrachlorideand polychloroethane; aliphatic hydrocarbons such as petroleumfractions, cyclohexane, light mineral oils, paraffins and kerosine;particularly suitable, however, are polar solutions ie. alcohols such asisopropanol, butanol, glycols, benzyl alcphol, furfuryl alcohols andcyclohexanol as-well as their ethers and esters; ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,-butyrolactone, and also dimethylformamide, dimethyl sulphoxide andN-methyl-pyrrolidone. Mixtures of different liquids are often suitable.

Suitable solid carriers include natural and synthetic clays andsilicates, for example natural silicas such as diatomaceous earths;magnesium silicates, for example talcs; magnesium aluminium silicates,for example attapulgites and vermiculites; aluminium silicates, forexample kaolinites, montmorillonites and micas; calcium carbonate;calcium sulphate; ammonium sulphate; synthetic hydrated silicon oxidesand synthetic calcium or aluminium silicates; elements, for examplecarbon and sulphur; natural and synthetic resins, for example coumaroneresins, polyvinyl chloride, and styrene polymers and copolymers; solidpolychlorophenols; bitumen; waxes; and solid fertilisers, for examplesuperphosphates. In particular, suitable solid carriers for powders ordusts include naturally occurring rock-flours, montmorillonite,kieselguhr or diatomite, and synthetic ground minerals such asmicro-dispersed silicic acid or aluminium oxide; suitable granulatecarriers include broken and graded natural rocks such as lime spar,marble, pumice, sepiolite and dolomite and synthetic granulates made oforganic and inorganic flours. In addition, granulates can be made fromorganic material such as sawdust, coconut shell flour, corncob fiber anddried tobacco stems.

Agricultural compositions are often formulated and transported in aconcentrated form which is subsequently diluted by the user beforeapplication. The presence of small amounts of a carrier which is asurface-active agent facilitates this process of dilution. Thuspreferably at least one carrier in a composition according to theinvention is a surface-active agent. For example the composition maycontain at least two carriers, at least one of which is a surface-activeagent.

A surface-active agent may be an emulsifying agent, a dispersing agentor a wetting agent; it may be nonionic or ionic. Examples of suitablesurface-active agents include the sodium or calcium salts of p6lyacrylicacids and lignin sulphonic acids; the condensation products of fattyacids or aliphatic amines or amides containing at least 12 carbon atomsin the molecule with ethylene oxide and/or propylene oxide; fatty acidesters of glycerol, sorbitol, sucrose or pentaerythritol; condensates ofthese with ethylene oxide and/or propylene oxide; condensation productsof fatty alcohol or alkyl phenols, for example p-octylphenol orp-octylcresol, with ethylene-oxide and/or propylene oxide; sulphates orsulphonates of these condensation products; alkali or alkaline earthmetal salts, preferably sodium salts, of sulphuric or sulphonic acidesters containing at least 10 carbon atoms in the molecule, for examplesodium lauryl sulphate, sodium secondary alkyl sulphates, sodium saltsof sulphonated castor oil, and sodium alkylaryl sulphonates such asdodecylbenzene sulphonate; and polymers of ethylene oxide and copolymersof ethylene oxide and propylene oxide. In particular, the following maybe used as emulsifiers and/or wetting agents: nonionic emulsifiers suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, polyoxyethyaene fatty amines, ethoxylated castor oil, andanionic emulsifiers such as acidic and neutralised alkylsulphonates,alkyl sulphates and aryl sulphonates. Lignin sulphite lyes andderivatised celluloses may be used as dispersants.

Binding agents such as carboxymethyl alcohol, natural water-solublepolymers such as gum arabic, and synthetic polymers in the form ofpowders, granules or latex such as polyvinyl alcohol or polyvinylacetate may be incorporated into the formulations.

The formulations may contain colourants in the form of inorganicpigments such as iron oxide, titanium oxide or prussian blue, or organicdyes such as alizarin, azo-dyes, metallic phthalocyanines ortriphenylmethane dyes. They may also contain odorisers eg. naturalperfume oils.

Depending on the type, the formulations preferably contain between 5%and 85% by weight of 30 active substance, preferably 20-80% by weight insolid formulations, 10-50% in formulations where the active substancesare in solution and 10-60% by weight where the active substances are insuspension.

Wettable powders usually contain 25, 50 or 75% w of active ingredientand usually contain in addition to solid inert carrier, 3-10% w of adispersing agent and, where necessary, 0-10% w of stabiliser(s) and/orother additives such as penetrants or stickers. Dusts are usuallyformulated as a dust concentrate having a similar composition to that ofa wettable powder but without a dispersant, and are diluted in the fieldwith further solid carrier to give a composition usually containing1/2-10% w of active ingredient. Granules are usually prepared to have asize between 10 and 100 BS mesh (1.676-0.152 mm), and may bemanufactured by agglomeration or impregnation techniques. Generally,granules will contain 1/2-75% w active ingredient and 0-10% w ofadditives such as stabilisers, surfactants, slow release modifiers andbinding agents. The so-called "dry flowable powders" consist ofrelatively small granules having a relatively high concentration ofactive ingredient. Emulsifiable concentrates usually contain, inaddition to a solvent and, when 20 necessary, co-solvent, 10-50% w/vactive ingredient, 2-20% w/v emulsifiers and 0-20% w/v of otheradditives such as stabilisers, penetrants and corrosion inhibitors.Suspension concentrates are usually compounded so as to obtain a stable,non-sedimenting flowable product and usually contain 10-75% w activeingredient, 0.5-15% w of dispersing agents,0.1-10% w of suspendingagents such as protective colloids and thixotropic agents, 0-10% w ofother additives such as defoamers, corrosion inhibitors, stabilisers,penetrants and stickers, and water or an organic liquid in which theactive ingredient is substantially insoluble; certain organic solids orinorganic salts may be present dissolved in the formulation to assist inpreventing sedimentation or as anti-freeze agents for water.

Aqueous dispersions and emulsions, for example compositions obtained bydiluting a wettable powder or a concentrate according to the inventionwith water, also lie within the scope of the invention. The saidemulsions may be of the water-in-oil or of the oil-in-water type, andmay have a thick `mayonnaise`-like consistency.

Products as described in the invention may be in the form of finishedformulations ie. in which the substances are already combined (seeExamples 1 to 11). However, the components of the combinations may alsobe supplied as separate formulations for mixing in the tank immediatelybefore application (see Examples 12-16). Concentrates according to theinvention are generally mixed with water to obtain the desiredconcentration of active substance.

The composition of the invention may also contain other ingredients, forexample other compounds possessing herbicidal, insecticidal orfungicidal properties. It is also possible to mix them with nematicides,bird repellents, growth regulators, plant nutrients or soilconditioners.

Of particular interest in enhancing the duration of the protectantactivity of the compounds of this invention is the use of a carrierwhich will provide a slow release of the fungicidal compounds into theenvironment of the plant which is to be protected. Such slow-releaseformulations could, for example, be inserted in the soil adjacent to theroots of a vine plant, or could include an adhesive component enablingthem to be applied directly to the stem of a vine plant.

The compositions are applied in the normal way; eg. by pouring,spraying, misting, dusting or scattering. The quantities to be appliedaccording to the invention may vary depending on weather conditions orthe state of the crop. The time to apply may be before or afterinfection. This is most important as in practice the point at whichinfection occurred cannot be recognised immediately. The duration ofprotection is normally dependent on the individual compound selected,and also a variety of external factors, such as climate, whose impact isnormally mitigated by the use of a suitable formulation.

The invention still further provides the use as a fungicide of acomposition as defined above, and a method for combating fungus at alocus, which comprises treating the locus, which may for example beplants subject to or subjected to fungal attack, seeds of such plants orthe medium in which such plants are growing or are to be grown, withsuch a composition.

The invention is illustrated in the following Examples.

Example

    ______________________________________    Emulsifiable concentrate formulation    ______________________________________    Phosphorous acid  22.3% by weight    β-(4-chlorophenyl)-β-(3,4-                      3.0% by weight    dimethoxyphenyl)acrylic acid    morpholide    sec-butylamine    9.7% by weight    Emulsifier (Na-alkyl benzene                      15% by weight    sulphonate)    Solvent (cyclohexanone)                      50% by weight    ______________________________________

Phosphorous acid is dissolved in the solvent and then the acrylic acidmorpholide is added. This produces a clear, bright yellow solution. Thesolution stays clear after the sec-butylamine and the emulsifier havebeen added.

Example

    ______________________________________    Wettable powder formulation    ______________________________________    Fosetyl-aluminum   50% by weight    β-(4-chlorophenyl)-β-(3,4                       10% by weight    dimethoxyphenyl)acrylic acid    morpholide    Wetting agent (alkylnaphthalene                       2% by weight    sulphonate)    Dispersant (lignin sulphonate)                       8% by weight    Carrier (kaolin)   30% by weight    ______________________________________

The components (all of which are solid) are mixed together and ground ina pinned disc mill until the particles are reduced to approx. 5-1 μm.

Example

    ______________________________________    Wettable powder formulation    ______________________________________    Disodum phosphite    50% by weight    β-(4-chlorophenyl)-β-(3,4-dimethoxy-                         5% by weight    phenyl)acrylic acid morpholide    Na-diisooctyl-sulpho-succinate                         2% by weight    (wetting agent)    Sodium sulphate (dispersant)                         10% by weight    Lignin sulphonate (dispersant)                         8% by weight    Kaolin (carrier)     25% by weight    ______________________________________

Na₂ HPO₃ is produced by neutralising H₃ PO₃ with NaOH in aqueoussolution and then spray drying.

The components are mixed thoroughly and ground in a pinned disc mill.

Example

    ______________________________________    Emulsifiable concentrate formulation    ______________________________________    Phosphorous acid       20% by weight    β-(4-biphenylyl)-β-(3,4-dimethoxyphenyl)-                           5% by weight    acrylic acid morpholide    Emulsifier (ethoxylated triylyceride)                           15% by weight    Solvent (diethylene glycol dimethyl                           60% by weight    ether)    ______________________________________

The phosporous acid is dissolved in the solvent and then the acrylicacid morpholide and the emulsifier are added. A clear solution isproduced.

Example

    ______________________________________    Wettable powder formulation    ______________________________________    Mancozeb (65%)         63% by weight    β-(3,4-dimethoxyphenyl)-β-(4-biphenylyl)-                           10% by weight    acrylic acid morpholide    Sodium sulphate        5% by weight    Kaolin (carrier)       12% by weight    Alkyl naphthalene sulphonate                           2% by weight    (wetting agent)    Lignin sulphonate (dispersant)                           8% by weight    ______________________________________

The ingredients are mixed and ground in a pinned disc mill.

Example

    ______________________________________    Suspension-emulsion concentrate formulation    ______________________________________    β-(4-biphenylyl)-β-(3,4-dimethoxyphenyl)-                           3% by weight    acrylic acid morpholide    Mancozeb (85%)         15% by weight    Lauryl alcohol polyglycol ether                           4% by weight    phosphate (emulsifier 1)    Ethoxylated triglyceride (emulsifier 2)                           2% by weight    Dodecyl benzene sulphonic acid,                           1.5% by weight    Ca-salt (emulsifier 3)    Ethylene oxide propylene oxide                           2.5% by weight    copolymer (dispersant)    Cyclohexanone          35% by weight    Alkyl aromatic fraction (boiling                           37% by weight    point > 200° C.)    ______________________________________

The acrylic acid morpholide is dissolved in 80% of the solvent, then theemulsifiers and the dispersants are added and the mixture is stirredthoroughly. After the Mancozeb is added, the mixture is ground in a beadmill (1 mm glass beads) and then the rest of the solvent is added.

Example

    ______________________________________    Aqueous suspension formulation    ______________________________________    β-(4-biphenylyl)-β-(3,4-dimethoxyphenyl)-                           15% by weight    acrylic acid morpholide    Dithianon (95%)        25% by weight    Dispersant (alkyl naphthalene                           2% by weight    sulphonate)    Stabiliser (hemicellulose)                           1% by weight    Antifreeze (propylene glycol)                           5% by weight    Water                  52% by weight    ______________________________________

The acrylic acid morpholide and the dithianon are ground in a bead mill(1 mm glass beads) together with 80% of the water and the dispersant.The other components are dissolved in the rest of the water and thenstirred into the other ingredients.

Example

    ______________________________________    Wettable powder formulation    ______________________________________    β- 4-(4-chlorophenoxy)phenyl!-β-                        5% by weight    (3,4-dimethoxyphenyl)-acrylic acid    morpholide    Chlorothalonil min (95%)                        40% by weight    Wetting agent (alkyl naphthalene                        2% by weight    sulphonate)    Carrier material (kieselguhr)                        20% by weight    Dispersant (lignin sulphonate)                        8% by weight    Filler (chalk)      25% by weight    ______________________________________

The acrylic acid morpholide is dissolved in acetone, and the solution isapplied to the carrier. The carrier is evaporated, the other ingredientsare crushed and added, and the mixture is ground in a pinned disc mill.

Example 10

The formulation in example 1 is tested biologically in a glass house incomparison with a 10% emulsifiable concentrate ofβ-(4-chlorophenyl)-β-(3,4-dimethoxyphenyl)-acrylic acid morpholide (I')and with phosphorus acid.

Test plants: grapevine seedlings at the 3-leaf stage (glass house)

Infection: plasmopara viticola

Application: 2 days after infection

A range of dosage rate concentrations was selected which would allowproper observation of the increase in effect.

    ______________________________________               Effect in % with a    Active     dosage rate in ppm of:    substance  100    747      50  374    25  188    ______________________________________    I'         51              58         30    phosphorous       6            8          0    acid    Combination               81              70         43    of both    substances    ______________________________________

Example 11

Effect Against Plasmopara Viticola

The active substances I' and fosetyl-aluminum were tested separately andin combination in the same way as in example 10.

    ______________________________________                     Dosage in ppm to achieve                     an effect of:    Active substance 50%     80%    ______________________________________    I'               100     >>100    fosetyl-aluminum >>1000  >>1000    I' +             25      100    fosetyl-aluminum 185     747    ______________________________________

Whilst 100 ppm I' only had a 50% effect and much more than 1000 ppm wererequired for the same effect with fosetyl-aluminum, a 50% effect wasachieved by combining 25 ppm I' and 188 ppm fosetyl: 100 ppm I' and 747ppm fosetyl-aluminum gave an effect of 80%.

Example 12

Effect on Pseudoperonospora Cubensis

I' and dithianon were tested separately and in combination for theireffect against pseudoperonospora cubensis on open grown cucumbers. Foursprayings were carried out at 7-day intervals.

    ______________________________________                 Dosage rate (ppm)                 required to achieve                 an effect of:    Active substance                 50%         72%    80%    ______________________________________    I'           250         800    >800    Dithianon    400         >750   >750    I' +                     100    300    dithianon                375    375    ______________________________________

Example 13

Effect on Phytophthora Infestans

I' and Mancozeb were tested separately and together (tank mixture) fortheir effect on phytophthora infestans in potatoes. Assessment was made4 weeks after final treatment. The table shows the effect in % whencertain concentrations of active substance were used.

    ______________________________________    ppm      0     800        1100 1600 (Mancozeb)    ______________________________________     0       0     11         24   47    100      0     18         48   49    150      0     24         53   57    200      0     23         51   63    (I')    ______________________________________

Whilst I' had no effect at the given dosages of 100, 150 and 200 ppm,the effect of 1600 ppm Mancozeb was increased to 63% when 200 ppm I' wasadded to it.

Example 14

Effect on Phytophthora Infestans

The test described in example 13 was also carried out withβ-(3,4-dimethoxyphenyl) -β(4-biphenylyl)-acrylic acid-morpholide(I.increment.) and Mancozeb. The results are given in the followingtable:

    ______________________________________    ppm     0           1100   1600 (Mancozeb)    ______________________________________    0       0           24     47    50      0           41     48    190     0           50     68    300     2           29     85    (I")    ______________________________________

Again, there is clear evidence of synergism.

Example 15

Effect Against Plasmopara Viticola

The active compounds β-(4-chlorophenyl)-β-3,4-dimethoxyphenyl)-acrylicacid morpholide (I') and fosetyl-aluminum were tested singly as well astheir combination.

    ______________________________________    Compound        Concentration                               Efficiency    ______________________________________    I'              100 ppm    58.1%    fosetyl-aluminum                    750 ppm    8.8%                    1000 ppm   8.1%    I' +            100 ppm    Al-phosethyl    750 ppm    84.4%    I' +            100 ppm    Al-phosethyl    1000 ppm   86.9%    ______________________________________

Example 16

Effect Against Plasmopara Viticola

The active compounds β-(4-chlorophenyl)-β-(3,4-dimethoxyphenyl)-acrylicacid morpholide (I') and cymoxanil were tested singly as well as theircombination.

    ______________________________________    Compound       Concentration                              Efficiency    ______________________________________    I'             80 ppm     35.0%    Cymoxanil      80 ppm     7.5%    I' +           80 ppm    Cymoxanil      80 ppm     58.8%    ______________________________________

NB. In Examples 15 and 16, % efficiency indicates the percentage ofuninfected leaves.

We claim:
 1. A compound of the formula: ##STR3## in which R₁ representsa hydrogen, chlorine, bromine, trifluoromethoxy, C₃₋₄ alkyl, C₃₋₄alkoxy, cyclohexyl, phenyl and R₂ represents a hydrogen atom.
 2. Acompound of the formula: ##STR4## in which R₁ represents a hydrogen,chlorine or bromine atom, a trifluoromethyl, trifluoromethoxy, C₃ -C₇alkyl, C₃ -C₅ alkoxy, C₃ -C₆ alkenyl, HClFC--CF₂ O--, HClC═CClO--,cyclohexyl, cyclopentenyl, cyclohexenyl, phenyl, 4-chlorophenyl,4-ethylphenyl, 4-chlorobenzyl or 4-chlorophenylthio group or a phenoxygroup optionally substituted by one or more substituents selected fromfluorine and chlorine atoms, methyl and ethoxycarbonyl groups and R₂represents a hydrogen atom, or R₁ represents a hydrogen atom and R₂represents a 3-phenoxy group.
 3. A compound according to claim 2,wherein R₂ is hydrogen.
 4. A compound according to claim 2, wherein R₂is 3-phenoxy.
 5. The compound β-(4-chlorophenyl)-β-(3,4-dimethoxyphenyl)acrylic acid morpholide.